Trisazo-dyestuffs



Patented Dec. 16, 1952 TRISAZO-DYESTUFFS Karl Menzi, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland,-a Swiss firm No Drawing. Application April 30, 1951, Serial N0. 2-2 3,823.v In Switzerland May- 16, 1950 Claims.

According. to this invention valuable new trisazo' dyestuffs are made by coupling an. aromatic met'adihyd'roxy-compound capable of coupling twice and containing at most. two fused 6,-mem-' bered. rings,. on the one hand. with. a. diazo compound of an amine of the formula there may be mentioned lzEl-dihydroxynaphthalene and especially 1:3-dihydroxybenzene.

The amines of' the'above formula contain in para-position. relatively to. theamino group or preferably in para-position to. the hydroxyl group the substituent X, which represents a CO'- alkyl or -CO-aryl' radical, but advantageously a' carboxylicacid arylideradicalbound to the benzene nucleus containing the amino and hydro'xyl groups by the CO"-group. The aryl radical present in the: carboxylic acid amide group may belongto thenaphthalene series or more especially the-benzene series. It may contain substituents, for example a. halogen atom such as chlorine, a lower alkyl or'alk-oxy roup such as a methyl, ethyl, methoxy or'ethoxygroup; The alkyl group present'in the -CO-a1kyl radical or many" radical likewise preferably contains only a few carbon atoms such, for example, as an ethyl or methyl group.

Asexamples of amines corresponding to the above formula and suitable as starting materials in the above process there may be mentioned:

3-amino-4-hydroxy-l-acetophenone,

(3-amino-4-hydroxy-pheny1) n-propyl-ketone,

(3-amino-4-hydroxy-phenyl) -ethyl-ketone,

l hydroxy 2 aminobenzene-5-carboxylic acid phenylamide,

1 hydroxy 2 aminobenzene 4 carboxylic acidl- (2'-chloro) -phenylamide,

l hydroxy 2 aminobenzene 4 carboxylic' acid- (3'-chloro) phenylamide,

1 hydroxy 2 aminobenzene 4 carboxylic' acid- (4-methyl) -phenylamide,

1 hydroxy 2 aminobenzene 4 carboxylic.

acid- (2--methoxy) -phenylamide,

1 hydroxy 2 aminobenzene 4 carboxylic' acid- 4'-ethoxy) -phenylamide,

1 hydroxy -'2 aminobenzene 4; carboxylic acid-naphthyl- (ll-amide,

1 hydroxy 2 aminobenzene 4 carboxylic acid-cyclohexylamide,

1 hydroxy. --2.- aminobenzene- 4 carboxylic acid-N-methyl-phenylamide,

Especially advantageous is l-hydroxy-Z- amino-benzene-4-carboxylic acid phenylamide.

A large number of such amines are known, and those which are not known can be made by methods in themselves known (compare, for example, U. S. Patents No. 2,467,621 and 2,538,568). The diazo compounds also used as starting materials in the present process are obtained by coupling tetrazotized 4:4-diamin'odiphenyl on one side with a 1-hydroxybenzene-2-carboxylic acid. As l-hydroxybenzene-2-carboxylic acids there come into consideration, for example, 5- or 6 methyl 1 hydroxybenzene-2-carb0xylic acid and above all l-hydroxybenzene-Z-carboxylic acid containing no further substituents. The coupling of the'tetrazotized 4:4'-diaminodiphenyl compounds with the hydroxybenzene ortho-carboxylic acids is carried out in known manner advantageously in a weakly alkaline medium, for. example. a-medium rendered alkaline with an alkali carbonate, and with the use of approximately equimolecular proportions of the tetrazo compound. of the am component.

Especially valuable trisazo dyestuifs ar'e 'obtamed by the present process whenall the starting materials are'free fromsulfonic acid'groups. The coupling of the aromatic m'eta-dihydroxy compound with the two different diazo com.- pounds may be carried out in either order of succession. However, it is in general of advantage to carry out the coupling with the diazo-azocompound in the second stage. Both couplings are advantageously carried out in an alkaline medium.

The dyestuffs obtainable by the present process arenew. They correspond to the general formula in which R1 represents the radical of an aromatic meta-dihydroxy-compound to which the hydroxyl groups are bound in positions vicinal to the azo groups and which contains at most two fused G-membered rings, R2 represents the radical of a 1-hydroxybenzene-2-carboxylic acid bound in the 4-position to the azo group, and X. represents a CO-alkyl radical present in paraposition relatively to one of the other two substituents, or a carboxylic acid arylide radical bound in para-position relatively to one of the two other substituents to the benzene nucleus B by the CO-group.

The dyestuffs of the invention are suitable for dyeing a very wide variety of materials, for example, animal fibers such as wool, silk and leather, but especially for dyeing or printing cellulose materials such as cotton, linen, or artificial silk or staple fibers of regenerated cellulose. The dyestufis may be treated on the fiber or partly on the fiber and partly in the dyebath with agents yielding metal by generally known methods. It is of advantage to use, for example, the process of U. S. Patent No. 2,148,659, in which first the dyeing and then the treatment with an agent yielding metal are carried out in the same bath. As agents yielding metal there come into consideration preferably those which are stable towards alkaline solutions, such as complex copper tartrates and the like.

In many cases especially valuable dyeings are obtained by working according to the process in which the dyeing or print produced with the V H O O H O H HO 0 V metal-free dyestuif is after-treated with an aqueous solution containing a basic condensation product of formaldehyde with a compound which contains at least once the atomic grouping Example 1 18.4 parts of 4:4-diaminodiphenyl are tetrazotized in'the usual manner with 13.8 parts of sodium nitrite, and coupled with 14.0 parts of 1- hydroxybenzene-Z-carboxylic acid in known manner in a medium rendered alkaline with sodium carbonate in order to form the diazoazo-compound. To the suspension of the resulting intermediate product is added at 3-12 C., a solution obtained by dissolving in 800 parts of water with the addition of 16 parts by volume of sodium hydroxide solution of 30 per cent. strength the monoaZo-dyestuff prepared as described below.

A suspension of 25.1 parts of 1-hydroxy-2- aminobenzene-4-carboxylic acid phenylamide in parts of water is cooled to 0 C. by the addition of ice and mixed with 27.5 parts of hydrochloric acid of 30 per cent. strength and 8 parts of sodium chloride. At 0-5 C. a solution of 7.6 parts of sodium nitrite in 25 parts of water is introduced dropwise, and the diazotization mixture is then stirred for about 20 minutes at 5-12 C. The solid diazonium compound is separated by filtration, washed with water until the filtrate no longer has an acid reaction to Congo, and suspended in a solution of 14.4 parts of 1:3- dihydroxybenzene and 1 part of concentrated hydrochloric acid in parts of water. For the purpose of coupling the resulting mixture is run at 5-10 C. into a solution of 40 parts of sodium carbonate in 300 parts of water. After stirring for 8 hours the monoazo-dyestuff is completely precipitated by the addition of sodium chloride and separated by filtration.

After stirring for 12 hours, the reaction solution is heated to 60C. and the trisazo-dyestufi is completely precipitated by the addition of sodium chloride.

The new dyestuff which corresponds to the formula is a dark powder having a slightly green bronze lustre, which dissolves in water, dilute sodium carbonate solution and dilute sodium hydroxide solution with a brown coloration. It dyes cotton by the single or 2-bath after-coppering process brown tints of very good fastness to light and excellent wet fastness properties.

By using in this example, instead of l-hydroxy-Z-aminobenzene-4-carboxylic acid phenylamide, an equimolecular quantity of 1) l hydroxy 2 aminobenzene-5-carboxylic acid phenylamide,

( 2) 1 hydroxy 2 aminobenzene-4-carboxylic acid- (2-chloro) -phenylamide,

(3) 1 hydroxy 2 aminobenzene-4-carboxylic acid- 3 -chloro) -phenylamide,

(4) 1 hydroxy 2 amino-benzene!-carboxylic acid- 4' -methyl) -phenylamide, (5) 1 hydroxy 2 amino-benzene-4-carboxylic acid- (2-methoxy) -phenylamide, (6) 1 hydroxy 2 aminobenzenel-carboxylic acid-cyclohexylamide,

(7) 1 hydroxy 2 aminobenzenei-carboxylic acid-naphthyl-l-amide,

(8) 1 hydroxy 2 aminobenzenei-carboxylic acid-N- nethylphenylamide or (9) 3 amino 4-hydroxy-l-acetophenone, there are obtained dyestufis of which the dyeings are similar to that of the dyestufi. described above both with regard to their tint and fastness properties. 7 7

These dyestuffs correspond to the formula 0 H O H HOOC azeaarzsa;

. wherein;ifi represents 'the radials of the above diazo components, viz. the following radicals- (listed inthe order given EbOVrOi di'azo compoof 1:3-dihydroxy-naphthalene, there. is'ohtained a dark powder which dissolves in waterand in d1- lute sodium carbonate solutionwith a browncoloration and in concentrated -sulfuric-acid witha violet coloration. This dyestutF'd-yes cotton-"by 61 the: single; or: z-bath after copperinga process brown tintss. having? an olive: shade* whichfhave very good properties of wet fastness and good fastness to light- Example 2 100 parts of cotton are entered at 50 C. into a. dyebath consisting of 4000 parts of water, 2 parts" of anhydrous sodium carbonate and 0:6 part ofthe dyestuff obtainable: as d'escribed'inthen-first four paragraphs of Example :1. temperature. is raised to 90-95 C. in the course of 20minutes, 30" parts of crystalline sodium sulfate are added and dyeing is carried on for 30 minutes at 90-100 C. The whole is then allowed tocool'to about 70C., 1.3 parts 01' complex sodium copper tartrate of approximately neutral reaction are added, coppering is carried onto! /2 hour at about C.', and-then the dyeingi isvrinsed with cold .water. If desired. the: dyeing "may be soaped by after-treatment with a solution containi'ngfi parts of soap and 2 'parts of anhydrous: sodium 'carbonatei'in: 1000: parts of water. A brown dyeing of very good "fastness-to. light and washing is obtained.

What is claimed is: 1. A' trisazo-dyestuif free from sulfonic acid groups and corresponding to the formula wherein R1 represents the radical ofan aromatic metadihydroxy'compound to which the-hydroxyl groups are. bound in positions vicinal'to the azo groups and which contains at most two fused sixemembered rings, R2 represents thewradical ofas lehydroxybenzene z carboxylic acid boundrin oat.

wherein R1 represents the radical of an aromatic inetadihydroxy compound to which the hydroxyl groups are bound in positions vicinal to the azo groups and which contains at most two fused six membered rings, R2 represents the radical of a l-'-hydroxybenzene-2-carboxylic acid bound in th'e' l' position to the azo group, and Y represents a carboxylic acid arylide radical bound to the benzene nucleus B by its -CO-groupand of 'which thenitrogen atom is substitutedby an aromatic radical containing atmost two: fused sixt-membered rings, and Y standsin para-position relatively to one of the other substituents ofi'the xbenzene nucleus B.

3;.A trlsazo-dyestufi free from sulfonic acid groups" and corresponding to the formula wherein R1 represents the radical of an aromatic metahydroxy compound to which the hydroxyl HOOC groups are bound in positions vicinal to the azo groups and which contains at most two fused six-membered rings, R2 represents the radical of a l-hydroxybenzene-Z-carboxylic acid bound in HOO tuted by a benzene radical.

4. Atrisazo-dyestufi free from sulfonic acid groups and corresponding to the formula OH HO wherein R2 represents the radical of a l-hydroxybenzene-2- carboxylic acid bound in 4-p0si- HOOC a a I HO 8 6. A trisazo-dyestuff corresponding to the formula 1 OH I HO wherein the radical of the 1:3-dihydroxybenzene is bound to the azo groups in ortho positions relatively to the hydroxyl groups.

7. A trisazo-dyestufi corresponding to the formula wherein the radical of the lza-dihydroxybenzene is bound to the azo groups in ortho positions relatively to the hydroxyl groups.

8. A trisazo-dyestufi corresponding to the formula mam-Q0113 wherein the radical of the 1:3-dihydroxybenzene is bound to the azo groups in ortho positions relatively to the hydroxyl groups.

9. A trisazo-dyestuff corresponding to the formula OH HO tion to the azo group, Z represents a benzene 45 wherein the radical of the 1:3-dihydroxybenzene radical, and the radical of the 1:3-dihydroxybenzene is bound to the azo groups in orthopositions relatively to the hydroxyl groups.

5. A trisazo-dyestufi free from sulfonic acid groups and corresponding to the formula is bound to the azo groups in ortho positions relatively to the hydroxyl groups.

10. A trisazo-dyestufi corresponding to the formula 0 OH HO wherein the radical of the 1:3-dihydroxybenzene HOOC the azo groups in ortho-positions relatively to the 6 hydroxyl groups.

REFERENCES CITED v 0-NHZ is bound to the azo groups in ortho positions relatively to the hydroxyl groups p KARL MEN-zr.

The following references are ofrecord in the file of this patent:

UNITED STATES PATENTS 

6. A TRISAZO-DYESTUFF CORRESPONDING TO THE FORMULA 